IP Library Granted Patent US 8,252,858
Granted Patent B2
US 8,252,858 · App. 11/770,072 · Granted Aug 28, 2012

Low smoke density poly(arylene ether) compositions, methods, and articles

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Quick Facts
Patent No.
US 8,252,858
App. No.
11/770,072
Granted
Aug 28, 2012
Kind
B2
Abstract

Thermoplastic compositions and methods of making the compositions are disclosed. The thermoplastic compositions include poly(arylene ether), a poly(alkenyl aromatic), an organophosphate ester flame retardant, a functionalized polysiloxane, and an organic acid. The thermoplastic compositions produce surprisingly low smoke density when burned, and they are useful for the fabrication of articles for the transportation and building and construction industries.

Claims (144)

1. A thermoplastic composition, comprising:

52.8 to 78.2 weight percent of a poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.33 to 0.46 deciliter per gram, measured at 25° C. in chloroform;

4.9 to 15 weight percent of a rubber-modified polystyrene;

4.86 to 9.5 weight percent of a polystyrene-polybutadiene-polystyrene triblock copolymer;

4.86 to 15.2 weight percent of an organophosphate ester flame retardant selected from the group consisting of bisphenol A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), and mixtures thereof;

2.8 to 4.7 weight percent of a functionalized polysiloxane comprising alkoxy substituents and aminoalkyl substituents comprising at least one primary or secondary amine; wherein the functionalized polysiloxane has a viscosity at 23° C. of 10 to 200 centistokes; and

0.46 to 1.43 weight percent of an organic acid selected from the group consisting of citric acid, fumaric acid, succinic acid, and maleic anhydride;

wherein the thermoplastic composition comprises less than 0.5 weight percent of polyamide;

wherein all weight percents are based on the total weight of the thermoplastic composition; and

wherein the thermoplastic composition has at least one smoke density property selected from the group consisting of

a smoke density at four minutes of 5 to 250 as determined by ASTM E662 at a sample thickness of 1.5 to 3.2 millimeters, and

a corrected maximum smoke density of 20 to 300 in the initial 20 minutes as determined by ASTM E662 at a sample thickness of 1.5 to 3.2 millimeters.

2. The thermoplastic composition of claim 1 , wherein the thermoplastic composition has a smoke density at four minutes of 5 to 250 as determined by ASTM E662 at a sample thickness of 3.2 millimeters.

3. The thermoplastic composition of claim 1 , wherein the thermoplastic composition has a corrected maximum smoke density of 20 to 300 in the initial 20 minutes as determined by ASTM E662 at a sample thickness of 3.2 millimeters.

4. The thermoplastic composition of claim 1 , wherein the thermoplastic composition further has a UL 94 rating of V-1 or V-0 at a sample thickness of 1.6 to 3.2 millimeters.

5. The thermoplastic composition of claim 1 , wherein the thermoplastic composition further has a UL 94 rating of V-1 or V-0 at a sample thickness of 1.0 to 1.6 millimeters.

6. The thermoplastic composition of claim 1 , wherein the thermoplastic composition has a UL 94 rating of V-0 at a sample thickness of 1.6 to 3.2 millimeters.

7. The thermoplastic composition of claim 1 , wherein the thermoplastic composition has a UL 94 rating of V-0 at a sample thickness of 1.0 to 1.6 millimeters.

8. The thermoplastic composition of claim 1 , wherein the thermoplastic composition has a notched Izod impact strength of at least 180 Joules per meter measured at 23° C. according ASTM D256.

9. The thermoplastic composition of claim 1 , wherein the thermoplastic composition has a notched Izod impact strength of 180 to 350 Joules per meter measured at 23° C. according ASTM D256.

10. The thermoplastic composition of claim 1 , wherein the functionalized polysiloxane comprises a 3-[(2-aminoethyl)amino]propyl group.

11. The thermoplastic composition of claim 1 , further comprising 0.1 to 3 weight percent of a linear low density polyethylene.

12. The thermoplastic composition of claim 1 , wherein the thermoplastic composition is substantially free of polyamides, polyesters, polyarylates, polyetherimides, and polycarbonates.

13. The thermoplastic composition of claim 1 , wherein the poly(2,6-dimethyl-1,4-phenylene ether) and the organic acid are provided in the form of melt-mixing poly(2,6-dimethyl-1,4-phenylene ether) and an organic acid selected from the group consisting of citric acid, fumaric acid, and maleic anhydride.

14. The thermoplastic composition of claim 1 , wherein the functionalized polysiloxane has the formula

wherein each occurrence of R 1 and R 2 is independently a C 1 -C 5 alkoxy substituent; R 3 is a C 1 -C 5 alkyl or a C 1 -C 10 aminoalkyl group comprising a primary amine or a secondary amine, provided that at least one occurrence of R 3 is a C 1 -C 10 aminoalkyl group comprising a primary amine or a secondary amine; each occurrence of R 4 is a C 1 -C 5 alkyl substituent or a bridging oxygen; x is 10 to 100; and y is 1 to 25.

15. The thermoplastic composition of claim 14 , wherein at least one occurrence of R 3 is 3-[(2-aminoethyl)amino]propyl.

16. The thermoplastic composition of claim 14 , wherein each occurrence of R 1 and R 2 is methoxy; each occurrence of R 3 is independently methyl or 3-[(2-aminoethyl)amino]propyl, provided that at least one occurrence of R 3 is 3-[(2-aminoethyl)amino]propyl; R 4 is a bridging oxygen or methyl; and y is 1 to 10.

17. A thermoplastic composition, comprising the reaction products obtained on melt kneading:

52.8 to 78.2 weight percent of a poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.33 to 0.46 deciliter per gram, measured at 25° C. in chloroform;

4.9 to 15 weight percent of a rubber-modified polystyrene;

4.86 to 9.5 weight percent of a polystyrene-polybutadiene-polystyrene triblock copolymer;

4.86 to 15.2 weight percent of an organophosphate ester flame retardant selected from the group consisting of bisphenol A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), and mixtures thereof;

2.8 to 4.7 weight percent of a functionalized polysiloxane comprising alkoxy substituents and aminoalkyl substituents comprising at least one primary or secondary amine; wherein the functionalized polysiloxane has a viscosity at 23° C. of 10 to 200 centistokes; and

0.46 to 1.43 weight percent of an organic acid selected from the group consisting of citric acid, fumaric acid, succinic acid, and maleic anhydride;

wherein the thermoplastic composition comprises less than 0.5 weight percent of polyamide;

wherein all weight percents are based on the total weight of the thermoplastic composition; and

wherein the thermoplastic composition has at least one smoke density property selected from the group consisting of

a smoke density at four minutes of 5 to 250 as determined by ASTM E662 at a sample thickness of 1.5 to 3.2 millimeters, and

a corrected maximum smoke density of 20 to 300 in the initial 20 minutes as determined by ASTM E662 at a sample thickness of 1.5 to 3.2 millimeters.

18. A thermoplastic composition, comprising:

60 to 78.2 weight percent of poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.35 to 0.45 deciliter per gram, measured at 25° C. in chloroform;

5 to 15 weight percent of a rubber-modified polystyrene;

4.86 to 9.5 weight percent of a polystyrene-polybutadiene-polystyrene triblock copolymer;

5 to 15 weight percent of bisphenol A bis(diphenyl phosphate);

2.8 to 4.7 weight percent of a functionalized polysiloxane having the formula

wherein each occurrence of R 3 is independently methyl or a 3-[(2-aminoethyl)amino]propyl group, provided that at least one occurrence of R 3 is a 3-[(2-aminoethyl)amino]propyl group; each occurrence of R 4 is independently methyl or a bridging oxygen; x is 10 to 100; and y is 1 to 10; and

0.46 to 1 weight percent of citric acid;

wherein the thermoplastic composition comprises less than 0.5 weight percent of polyamide; and

wherein all weight percents are based on the total weight of the composition; and

wherein the thermoplastic composition has

a smoke density at four minutes of 5 to 250 as determined by ASTM E662 at a sample thickness of 3.2 millimeters,

a corrected maximum smoke density of 20 to 300 in the initial 20 minutes as determined by ASTM E662 at a sample thickness of 3.2 millimeters, and

a UL 94 rating of V-0 at a sample thickness of 1.6 to 3.2 millimeters.

19. The thermoplastic composition of claim 18 , wherein the thermoplastic composition has a notched Izod impact strength of 180 to 350 Joules per meter measured at 23° C. according ASTM D256.

20. A thermoplastic composition, consisting of:

60 to 78.2 weight percent of poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.35 to 0.45 deciliter per gram, measured at 25° C. in chloroform;

5 to 15 weight percent of a rubber-modified polystyrene;

4.86 to 9.5 weight percent of a polystyrene-polybutadiene-polystyrene triblock copolymer;

5 to 15 weight percent of bisphenol A bis(diphenyl phosphate);

2.8 to 4.7 weight percent of a functionalized polysiloxane having the formula

wherein each occurrence of R 3 is independently methyl or a 3-[(2-aminoethyl)amino]propyl group, provided that at least one occurrence of R 3 is a 3-[(2-aminoethyl)amino]propyl group; R 4 is a bridging oxygen or methyl; x is 10 to 100; and y is 1 to 10;

0.46 to 1 weight percent of citric acid; and

optionally, up to 5 weight percent of an additive selected from the group consisting of stabilizers, processing aids, drip retardants, nucleating agents, dyes, pigments, antioxidants, anti-static agents, blowing agents, metal deactivators, antiblocking agents, fragrances, and combinations thereof;

wherein the thermoplastic composition comprises less than 0.5 weight percent of polyamide;

wherein all weight percents are based on the total weight of the composition; and

wherein the thermoplastic composition has

a smoke density at four minutes of 5 to 250 as determined by ASTM E662 at a sample thickness of 3.2 millimeters,

a corrected maximum smoke density of 20 to 300 in the initial 20 minutes as determined by ASTM E662 at a sample thickness of 3.2 millimeters, and

a UL 94 rating of V-0 at a sample thickness of 1.6 to 3.2 millimeters.

21. The thermoplastic composition of claim 20 , wherein the thermoplastic composition has a notched Izod impact strength of 180 to 350 Joules per meter measured at 23° C. according ASTM D256.

22. An article comprising a thermoplastic composition comprising:

52.8 to 7.2 weight percent of a poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.33 to 0.46 deciliter per gram, measured at 25° C. in chloroform;

4.9 to 15 weight percent of a rubber-modified polystyrene;

4.86 to 9.5 weight percent of a polystyrene-polybutadiene-polystyrene triblock copolymer;

4.86 to 15.2 weight percent of an organophosphate ester flame retardant selected from the group consisting of bisphenol A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), and mixtures thereof;

2.8 to 4.7 weight percent of a functionalized polysiloxane comprising alkoxy substituents and aminoalkyl substituents comprising at least one primary or secondary amine; wherein the functionalized polysiloxane has a viscosity at 23° C. of 10 to 200 centistokes; and

0.46 to 1.43 weight percent of an organic acid selected from the group consisting of citric acid, fumaric acid, succinic acid, and maleic acid;

wherein the thermoplastic composition comprises less than 0.5 weight percent of polyamide;

wherein all weight percents are based on the total weight of the thermoplastic composition; and

wherein the thermoplastic composition has at least one smoke density property selected from the group consisting of

a smoke density at four minutes of 5 to 250 as determined by ASTM E662 at a sample thickness of 1.5 to 3.2 millimeters, and

a corrected maximum smoke density of 20 to 300 in the initial 20 minutes as determined by ASTM E662 at a sample thickness of 1.5 to 3.2 millimeters.

23. An article comprising a thermoplastic composition comprising:

60 to 78.2 weight percent of poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.35 to 0.45 deciliter per gram, measured at 25° C. in chloroform;

5 to 15 weight percent of a rubber-modified polystyrene;

4.86 to 9.5 weight percent of a polystyrene-polybutadiene-polystyrene triblock copolymer;

5 to 15 weight percent of bisphenol A bis(diphenyl phosphate);

2.8 to 4.7 weight percent of a functionalized polysiloxane having the formula

wherein each occurrence of R 3 is independently methyl or a 3-[(2-aminoethyl)amino]propyl group, provided that at least one occurrence of R 3 is a 3-[(2-aminoethyl)amino]propyl group; each occurrence of R 4 is independently methyl or a bridging oxygen; x is 10 to 100; and y is 1 to 10; and

0.46 to 1 weight percent of citric acid;

wherein the thermoplastic composition comprises less than 0.5 weight percent of polyamide; and

wherein all weight percents are based on the total weight of the composition; and

wherein the thermoplastic composition has

a smoke density at four minutes of 5 to 250 as determined by ASTM E662 at a sample thickness of 3.2 millimeters,

a corrected maximum smoke density of 20 to 300 in the initial 20 minutes as determined by ASTM E662 at a sample thickness of 3.2 millimeters, and

a UL 94 rating of V-0 at a sample thickness of 1.6 to 3.2 millimeters.

24. An article comprising a thermoplastic composition consisting of:

60 to 78.2 weight percent of poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.35 to 0.45 deciliter per gram, measured at 25° C. in chloroform;

5 to 15 weight percent of a rubber-modified polystyrene;

4.86 to 9.5 weight percent of a polystyrene-polybutadiene-polystyrene triblock copolymer;

5 to 15 weight percent of bisphenol A bis(diphenyl phosphate);

2.8 to 4.7 weight percent of a functionalized polysiloxane having the formula

wherein each occurrence of R 3 is independently methyl or a 3-[(2-aminoethyl)amino]propyl group, provided that at least one occurrence of R 3 is a 3-[(2-aminoethyl)amino]propyl group; R 4 is a bridging oxygen or methyl; x is 10 to 100; and y is 1 to 10;

0.46 to 1 weight percent of citric acid; and

optionally, up to 5 weight percent of an additive selected from the group consisting of stabilizers, processing aids, drip retardants, nucleating agents, dyes, pigments, antioxidants, anti-static agents, blowing agents, metal deactivators, antiblocking agents, fragrances, and combinations thereof;

wherein the thermoplastic composition comprises less than 0.5 weight percent of polyamide;

wherein all weight percents are based on the total weight of the composition; and

wherein the thermoplastic composition has

a smoke density at four minutes of 5 to 250 as determined by ASTM E662 at a sample thickness of 3.2 millimeters,

a corrected maximum smoke density of 20 to 300 in the initial 20 minutes as determined by ASTM E662 at a sample thickness of 3.2 millimeters, and

a UL 94 rating of V-0 at a sample thickness of 1.6 to 3.2 millimeters.

25. A method of preparing a thermoplastic composition, comprising:

melt kneading

52.8 to 78.2 weight percent of a poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.33 to 0.46 deciliter per gram, measured at 25° C. in chloroform,

4.9 to 15 weight percent of a rubber-modified polystyrene,

4.86 to 9.5 weight percent of a polystyrene-polybutadiene-polystyrene triblock copolymer,

4.86 to 15.2 weight percent of an organophosphate ester flame retardant selected from the group consisting of bisphenol A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), and mixtures thereof,

2.8 to 4.7 weight percent of a functionalized polysiloxane comprising alkoxy substituents and aminoalkyl substituents comprising at least one primary or secondary amine, wherein the functionalized polysiloxane has a viscosity at 23° C. of 10 to 200 centistokes, and

0.46 to 1.43 weight percent of an organic acid selected from the group consisting of citric acid, fumaric acid, succinic acid, and maleic anhydride

to form a thermoplastic composition;

wherein the thermoplastic composition comprises less than 0.5 weight percent of polyamide;

wherein all weight percents are based on the total weight of the thermoplastic composition; and

wherein the thermoplastic composition has at least one smoke density property selected from the group consisting of

a smoke density at four minutes of 5 to 250 as determined by ASTM E662 at a sample thickness of 1.5 to 3.2 millimeters, and

a corrected maximum smoke density of 20 to 300 in the initial 20 minutes as determined by ASTM E662 at a sample thickness of 1.5 to 3.2 millimeters.

26. The method of claim 25 , wherein the melt kneading is conducted on an extruder comprising a vacuum vent in the downstream one third of the extruder; and wherein the vacuum vent is maintained at a vacuum of 30 to 76 centimeters of mercury.

27. A method of preparing a thermoplastic composition, comprising:

melt kneading

60 to 78.2 weight percent of poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.35 to 0.45 deciliter per gram, measured at 25° C. in chloroform,

5 to 15 weight percent of a rubber-modified polystyrene,

4.86 to 9.5 weight percent of a polystyrene-polybutadiene-polystyrene triblock copolymer,

5 to 15 weight percent of bisphenol A bis(diphenyl phosphate),

2.8 to 4.7 weight percent of a functionalized polysiloxane having the formula

wherein each occurrence of R 3 is independently methyl or a 3-[(2-aminoethyl)amino]propyl group, provided that at least one occurrence of R 3 is a 3-[(2-aminoethyl)amino]propyl group, R 4 is a bridging oxygen or methyl, x is 10 to 100, and y is 1 to 10, and

0.46 to 1 weight percent of citric acid

to form a thermoplastic composition;

wherein the thermoplastic composition comprises less than 0.5 weight percent of polyamide;

wherein all weight percents are based on the total weight of the composition; and

wherein the thermoplastic composition has

a smoke density at four minutes of 5 to 250 as determined by ASTM E662 at a sample thickness of 3.2 millimeters,

a corrected maximum smoke density of 20 to 300 in the initial 20 minutes as determined by ASTM E662 at a sample thickness of 3.2 millimeters, and

a UL 94 rating of V-0 at a sample thickness of 1.6 to 3.2 millimeters.

28. The method of claim 27 , wherein the melt kneading is conducted on an extruder comprising a vacuum vent in the downstream one third of the extruder; and wherein the vacuum vent is maintained at a vacuum of 30 to 76 centimeters of mercury.

Assignments (7)
CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE THE APPLICATION NUMBER 15039474 PREVIOUSLY RECORDED AT REEL: 054528 FRAME: 0467. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Mar 23, 2021
From: SABIC GLOBAL TECHNOLOGIES B.V.
To: SHPP GLOBAL TECHNOLOGIES B.V.
Reel/Frame 057453/0680 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 26, 2020
From: SABIC GLOBAL TECHNOLOGIES B.V.
To: SHPP GLOBAL TECHNOLOGIES B.V.
Reel/Frame 054528/0467 →
CHANGE OF NAME Recorded Jun 6, 2016
From: SABIC INNOVATIVE PLASTICS IP B.V.
To: SABIC GLOBAL TECHNOLOGIES B.V.
Reel/Frame 038883/0816 →
RELEASE OF SECURITY INTEREST Recorded Mar 17, 2014
From: CITIBANK, N.A.
To: SABIC INNOVATIVE PLASTICS IP B.V.
Reel/Frame 032459/0798 →
SECURITY AGREEMENT Recorded Aug 18, 2008
From: SABIC INNOVATIVE PLASTICS IP B.V.
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 021423/0001 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 1, 2008
From: GENERAL ELECTRIC COMPANY
To: SABIC INNOVATIVE PLASTICS IP B.V.
Reel/Frame 020985/0551 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 3, 2007
From: KISHORE, AVADHANULA VENKATA SUBRAMANYA; BAJGUR, CHANDRA SEKHAR; DHANABALAN, ANANTHARAMAN; MHETAR, VIJAY; MOHITE, AMOL ADHIKRAO; NAMJOSHI, ABHIJIT ANAND; SANGAJ, NIVEDITA SHISHUPAL; SHARMA, KIRTI; SAVARNA, SUMI
To: GENERAL ELECTRIC COMPANY
Reel/Frame 019642/0978 →